Diffusion transfer photographic materials

ABSTRACT

A TONING AGENT REPRESENTED BY THE GENERAL FORMULA   2-(X-CH2-),3-(S=),4-R,5-R&#39;&#39;-2,3-DIHYDRO-4H-TRIAZOLE   2-((3-(S=),4-R,5-R1-2,3-DIHYDRO-4H-TRIAZOL-2-YL)-CH2-   Y-CH2-),3-(S=),4-R,5-R&#39;&#39;-2,3-DIHYDRO-4H-TRIAZOLE   WHEREIN R AND R1 EACH REPRESENTS A HYDROGEN ATOM, A LOWER ALKYL GROUP OR AN ARYL GROUP; X REPRESENTS A HYDROXYL GROUP AND   -N(-R1)-R2   (WHERE R1 AND R2 EACH REPRESENTS A LOWER ALKYL GROUP OR ARYL GROUP AND R1 AND R2 MAY TOGETHER COMPLETE A HETEROCYCLIC RING); AND Y REPRESENTS   -N(-R3)-   (WHERE R3 REPRESENTS A LOWER ALKYL GROUP OR AN ARALKYL GROUP), IS USED IN DIFFUSION TRANSFER PHOTOGRAPHIC MATERIAL TO GIVE DEEP BLACK IMAGES OR PRINTINGS ON A POSITIVE MATERIAL IN DIFFISION TRANSFER PHOTOGRAPHY.

United States Patent 3,577,240 DIFFUSION TRANSFER PHOTOGRAPHIC MATERIALS Fumihiko Nishio, Odawara-shi, and Reiichi Ohi and Tatsuyo Tajima, Minamiashigara-machi, Japan, assignors to Fuji Shashin Film Kabushiki Kaisha,

, Ashigarakami-gun, Kanagawa-ken, Japan No Drawing. Continuation-impart of application Ser. No. 431,453, Feb. 9, 1965. This application Oct. 24, 1968,

Ser. No. 770,412

Int. Cl. G03c 7/00 US. Cl. 9652 ABSTRACT OF THE DISCLOSURE A toning agent represented by the general formula wherein R and R each represents a hydrogen atom, a lower alkyl group or an aryl group; X represents a hydroxyl group and This application is a continuation-in-part of application Ser. No. 431,453 filed Feb. 9, 1965, now abandoned.

The present invention relates to an improved diffusion transfer photographic material and more particularly the invention relates to a composition of a diffusion transfer 12 Claims photographic material containing one or more novel toning agents. It should however be understood that the term 'diffusion transfer photographic material in the specification and the claims of this invention means a negative material and a positive material as Well as a developer for diffusion transfer photography.

A diffusion transfer photographic process is generally represented by the process wherein a negative material having a silver halide photographic sensitive layer is printed with an original pattern, the printed negative map terial is closely contacted under the presence of a developing solution with a positive material having an image accepting layer containing colloidal silver or silver sulfide as a development nuclei that can reduce silver complex in the layer. The developing solution develops the silver ha- I lide at the exposed portions of the photographic sensi-' tive layer and dissolves the silver halide into silver complex at the unexposed portions of the photographic sensitive layer. The silver complex is diffused into the image accepting layer of the positive material and deposited there as reduced silver. After the contact the positive material is stripped from the negative material to give the positive material having printing 'of the original pattern.

If in such a process, however, a toning agent, which influences the deposition of reduced silver in the image accepting layer, is not used, the image formed on the image accepting layer becomes yellow or brown and a deep black image or printing cannot be obtained.

An object of this invention is to pr'ovide novel and improved agents for giving .deep black images or printings on a positive material in diffusion transfer photography.

Another object of this invention is to provide a diffusion transfer photographic material containing the novel and improved toning agents.

A further object of this invention is to provide deep black images or printings on a positive material by a diffusion transfer photography using novel and improved toning agents.

Other objects and advantages of the present invention Will be apparent to those skilled in the art as the description and illustration thereof proceed.

In accordance with the present invention, in at least one of a silver halide emulsion layer, an image accepting layer and a developing solution for diffusion transfer photography is added as a toning agent at least one compound shown by the general formula wherein R and R each represents a hydrogen atom, a. lower alkyl group, or an aryl group; X represents a hydroxyl group or.

(R and R each represents a lower alkyl group or an aryl group and R and R may complete a heterocyclic ring), and Y represents (R represents a lower alkyl group or an aralkyl group). The preferred examples of the compounds shown by the above general formula are as follows:

COMPOUND 1 3 -morpholinomethyll phenyll,3,4-triazol-4 in-2-thione COMPO UND 2 -methyl-3-morpholinomethyl-1-phenyl-1,3,4-

triazol-4-in-2-thione CHzCHz N--N-C HzN ll CHa-C C=S CHzCH:

COMPOUND 3 N-isopropyl-N,N-bis(1,5-dimethyl)-1,3,4-triazol- 4-in-2-thion-3-yl-methy1) amine N-benzy1-N,N-bis( 1-methyl-1,3,4-triazol-4- in-2-thion-3-yl-methyl) amine 3-hydroxymethy1-5 -methyl-1,3,4-triazol-4- in-Z-thione ll CHr-C C S COMPOUND 6 3-diethylaminomethyl-S-phenyl-1,3,4-

triazol-4-in-2-thione N-N C HzN Q-(J C: S C 2H5 1';

COMPOUND 7 3-piperidinomethyl-l-phenyl-l,3,4- triazol-4-in-2-thione CHzCHz 4 COMPOUND s 1-methyl-3 -thiamorpholinomethyl-1,3,4- triazol-4-in-2-thione The compounds used as toning agents can be produced by the general method disclosed in Chemical Abstracts, volume 54 (1960), in columns 2.4664(i) and 24665 a and b). By means of this known reaction, a compound having a five membered heterocyclic ring containing a 2-mercapto group and a nitrogen atom in the 3-position, is reacted with Formalin and an amine (or alcohol) to convert the Z-mercapto group to a double-bonded sulfur (=8) and to attach an aminomethyl (or hydroxymethy-l) group to the nitrogen atom in the 3-position. The reaction is illustrated as follows:

alcohol) ircHramme residue (or alcohol residue) Thus, Compounds 1-8 are produced by the same reaction merely by using the desired Z-mercaptotriazole, which is a compound having a five membered heterocyclic ring containing a Z-mercapto group and a nitrogen atom in the 3-position, instead of the Z-mercaptobenzo- (1) Synthesis of Compound 1 A mixture of 18.7 g. of l-phenyl-Z-mercapto-1,3,4-triazole crystals, 7.5 ml. of 37% Formalin and 20 ml. of ethanol was warmed on a hot bath to melt the crystals. Then, after warming for 5 minutes, 8.7 g. of morpholine were added. The mixture was then warmed for 10 minutes and left to be cooled. The crystals thus produced were filtered out and recrystallized with ethanol to give 19.3 g. of white crystals. M.P. 149150 C.

(2) Synthesis of Compound 2 A mixture of 19.1 g. of 1-phenyl-2-mercapto-5-methyl- 1,3,4-triazole crystals, 7.5 ml. of 37% Formalin and 20 ml. of ethanol was warmed on a hot bath to melt the crystals. Then, after warming for 5 minutes, 8.7 g. of morpholine were added. The mixture was then warmed for 10 minutes and left to be cooled. The crystals thus produced were filtered out and recrystallized with ethanol to obtain 21.0 g. of white crystals. M.P. 186-l 87 C.

(3) Synthesis of Compound 3 A mixture of 12.9 g. of 1,S-dimethyl-Z-mercapto-1,3,4- triazole crystals, 7.5 ml. of 37% Formalin and 20 ml. of ethanol was warmed on a hot bath to melt the crystals.

Then, after warming for minutes, 3 g. of isopropylamine were added. The mixture was then warmed for minutes and left to be cooled. The crystals thus produced were recrystallized with methanol to obtain 5.6 g. of white crystals. M.P. 182-l83 C.

'(4) Synthesis of Compound 4 A mixture of 11.5 g. of 1-methyl-2-mercapto-1,3,4-triazole crystals, 75 ml. of 37% Formalin and ml. of ethanol was warmed on a hot bath to melt the crystals. Then, after warming for 5 minutes, 5.5 g. of benzylamine were added. The mixture was then warmed for 10 minutes and left to be cooled. The crystals thus produced were recrystallized with ethanol to obtain 12.5 g. of white crystals. M.P. l20-122 C.

(5) Synthesis of Compound 5 A mixture of 2.3 g. of l-mercapto-S-methyl-l,3,4-triazole, 2.5 ml. of 37 Formalin and 10 ml. of ethanol was warmed on a hot bath to melt the crystals. Then, after warming for 5 minutes, it was heated under reduced pressure to distil out the solvent and left to be dried. The crystals thus produced were washed in a small quantity of methanol and dried. 1.5 g. of white crystals were obtained. M.P. 155-157 C.

(6) Synthesis of Compound 6 A mixture of 3.7 g. of 2-mereapto-5-phenyl-1,3,4-triazole crystals, 7.5 ml. of 37% Formalin and 10 ml. of ethanol was warmed on a hot bath to melt the crystals. Then, after warming for 5 minutes, 1.5 g. of diethyl amine were added. The mixture was warmed for 10 minutes and then heated under reduced pressure to distil out the solvent and dried 5.3 g. of the syrup-like product were obtained.

(7) Synthesis of Compound 7 A mixture of 18.7 g. of 1-phenyl-2-mercapto-1,3,4-triazole crystals, 7.5 ml. of 37% Formalin and 20 ml. of ethanol was warmed on a hot bath to melt the crystals. Then, after warming for 5 minutes, 8.5 g. of piperidine were added. The mixture was then warmed for 10 minutes. A syrup-like substance obtained by distilling out the solvent was left for 2 days to produce a small amount of crystals. These crystals were mixed with methanol. From this mixture the crystals were filtered out and recrystallized with ethanol. 8.9 g. of white crystals were obtained. M.P. 88- 90 C.

(8) Synthesis of Compound 8 A mixture of 1.9 g. of l-methyl-Z-mercapto-l,3,4-triazole crystals, 0.75 ml. of 37% Formalin and 5 ml. of ethanol was warmed on a hot bath to melt the crystals. Then, after warming for 5 minutes, 1.0 g. of thiomorpholine was added. The mixture was warmed for 10 minutes and then the solvent was dsitilled out by heating under reduced pressure. 2.8 g. of a syrup-like product were obtained.

The suitable amount of the toning agent of this invention is, when it is added in a developing solution for diffusion transfer photography, about 0.001 g. to about 1 g., preferably about 0.005 g. to about 0.05 g., per 1 liter of developing solution; when it is added in a silver halide emulsion, about 0.001 g. to about 1 g., preferably about 0.05 g. to about 0.5 g. per 1 kg. of emulsion; and when it is added in a positive material having an image accepting layer, about 0.001 g. to about 1 g., preferably about 0.05 g. to about 0.5 g. per 1 liter of coating liquid for the image accepting layer.

The toning agent of this invention may be added in a diffusion transfer photographic material alone or as a mixture of the compounds shown by the above general formula. Further, the toning agent of this invention may be added in one, two or all three of the following diffusion transfer photographic materials: the photosensitive emulsion layer; the image accepting layer; and the developing solution. However, in the case where the toning agent is added in two of the materials, e.g., in the silver halide emulsion layer of a negative material and the image accepting layer of a positive material, the amount of the toning agent added to each layer may be less than where it is added in only one layer. This is true when the toning agent is added in one of the layers and in the developing solution or in two layers and in the developing solution simultaneously.

The binder for the silver halide emulsion layer and the image accepting layer may be gelatin, a material other than gelatin, or mixture thereof.

The invention will now be explained further in detail by the following examples but it should be understood that the invention is not limited to them.

EXAMPLE 1 A negative material was prepared by coating on a photographic paper a high contrast silver chloride emulsion such that the coated layer had the following composition:

G./sq. 111. Silver chloride 1.2 Benzotriazole 0.005 Hydroquinone 0.2 Gelatin 4.2

An original pattern to be copied was exposed on the dried emulsion layer of the negative material and the layer was treated with a developing solution having the following composition:

G. Hydroquinone 12 1-phenyl-3-pyrazolidone 0.5 Anhydrous sodium sulfite 7 Sodium hydroxide 15 Water to make 1 liter.

In the developing solution or after developing the emulsion layer of the negative material containing the developing solution was closely contacted with an image accepting layer of a positive material for about 20 seconds. The positive material consisted of a support paper and the image accepting layer coated on the paper and having the following composition:

G./sq. m. Gelatin 5 Anhydrous sodium thiosulfate 1.5 Starch 0.5 Colloidal silver sulfide 0.002 Compound 1 0.2

When the positive material was stripped from the negative material, a deep black positive image was obtained on the positive material.

EXAMPLE 2 The similar treatment to Example 1 was conducted while replacing benzotriazole in the negative material in Example 1 with Compound 2 (0.05 g./sq. m.) and removing Compound 1 in the positive material, and a deep black positive image was also obtained.

EXAMPLE 3 An original pattern was exposed by reflection method on the negative material in Example 1 and the material was developed with a developing solution having the fol lowing composition:

G. Hydroquinone 18 1-phenyl-3-pyrazolidone 0.5 Compound 5 0.05 Anhydrous sodium sulfite 60 Anhydrous sodium. thiosulfate 8 Sodium hydroxide 14 Water to make 1 liter.

As in Example 1, the negative emulsion layer containing the developing solution was closely contacted with an 7 image accepting layer of a positive material, said image accepting layer having the following composition:

G./sq. m. Gelatin 4 Polyvinyl alcohol 1.5 Compound 4 0.06 Barium sulfate 0.4 Colloidal palladium sulfate 0.003

In this case, the support for the positive material may be a paper or a transparent base.

When the positive material was stripped from the negative material, a deep black positive image was obtained on the image accepting layer of the positive material.

By the embodiment shown in the example the scums on the surface of thus formed positive image do not appear.

EXAMPLE 4 The treatment similar to Example 3 was conducted while replacing Compound 5 in the developing solution in Example 3 with Compound 1 (002 g./liter) and replacing Compound 4 in the image accepting layer of the positive material with Compound 6 (0.05 g./sq. m.), and a deep black positive image was also obtained.

What is claimed is:

1.. A diffusion transfer photographic material containing at least one toning agent selected from the group consisting of the compounds shown by the general formula N N-CHrX where R and R each represents a member selected from the group consisting of a lower alkyl group and an aryl group and R and R may together complete a heterocyclic ring; and Y represents where R represents a member selected from the group consisting of a lower alkyl group and aralkyl group.

2. The diffusion transfer photographic material according to claim 1 wherein said material is a negative material for diffusion transfer photography and said toning agent is incorporated in a silver halide emulsion layer of the material in an amount of about 0.001 g. to about 1 g. per 1 kg. of said silver halide emulsion.

3. The diffusion transfer photographic material according to claim 1 wherein said material is a positive material for diffusion transfer photography and said toning agent is incorporated in an image accepting layer of the positive material in an amount of about 0.001 g. to about 1 g. per 1 liter of the coating liquid for said layer.

4. The diffusion transfer photographic material according to claim 1 wherein said material is a developing solution .for diffusion transfer photography and said toning agent is incorporated in said solution in an amount of about 0.001 g. to about 1 g. per liter of said solution.

5. The diffusion transfer photographic material accordingto claim 1 wherein said toningagent is a compound shown by the formula I 6. The diffusion transfer photographic material according to claim 1 wherein said toning agent is a compound shown by the formula 7. The diffusion transfer photographic material according to claim 1 wherein said toning agent is a compound shown by the formula l C H3 CH3 8. The diffusion transfer photographic material according to claim 1 wherein said toning agent is a compound shown by the formula 9. The diffusion transfer photographic material accordingto claim 1 wherein said toning agent is a compound shown by the formula I I1- Icrnon" 10.'The diffusion transfer photographic material according to claim 1 wherein said toning agent is a compound shown by the formula N--NCHzN 3 O 9 10 11. The dilfusion transfer photographic material according to claim 1 wherein said toning agent is a comcording to claim 1 wherein said toning agent is a compound shown by the formula pound shown by the formula CHZCH2 H(\ G=S \CH2CH2 01120112 I lf-lf-omn cm CH; K CHaCHQ 10 References Cited N Chemical Abstracts, vol. 54, 24663 (t)24664(b) 1960.

I Stavrovskaya et al., Zhurnal Obshchei Khimii, 30, 689- 15 WILLIAM D. MARTIN, Primary Examiner H. J. GWINNELL, Assistant Examiner US. Cl. X.R. 12. The diffusion transfer photographic material ac- 96 29,77,96 

